CN114409380A - Method for recycling ITO target material waste - Google Patents
Method for recycling ITO target material waste Download PDFInfo
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- CN114409380A CN114409380A CN202210029115.8A CN202210029115A CN114409380A CN 114409380 A CN114409380 A CN 114409380A CN 202210029115 A CN202210029115 A CN 202210029115A CN 114409380 A CN114409380 A CN 114409380A
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- ito
- sintering
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- 238000000034 method Methods 0.000 title claims abstract description 49
- 239000002699 waste material Substances 0.000 title claims abstract description 31
- 238000004064 recycling Methods 0.000 title claims abstract description 23
- 239000013077 target material Substances 0.000 title abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 54
- 229910003437 indium oxide Inorganic materials 0.000 claims abstract description 34
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims abstract description 34
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000005238 degreasing Methods 0.000 claims abstract description 12
- 238000012216 screening Methods 0.000 claims abstract description 6
- 238000005245 sintering Methods 0.000 claims description 45
- 239000002245 particle Substances 0.000 claims description 29
- 238000010438 heat treatment Methods 0.000 claims description 27
- 239000002270 dispersing agent Substances 0.000 claims description 26
- 239000002002 slurry Substances 0.000 claims description 15
- 230000001804 emulsifying effect Effects 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000004321 preservation Methods 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000011268 mixed slurry Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 8
- 238000004945 emulsification Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 150000001414 amino alcohols Chemical class 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 238000009694 cold isostatic pressing Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims 2
- 238000007873 sieving Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 238000000498 ball milling Methods 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 3
- 229910052738 indium Inorganic materials 0.000 abstract description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 238000001694 spray drying Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000000523 sample Substances 0.000 description 3
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000003921 particle size analysis Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- C04B35/62204—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products using waste materials or refuse
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Abstract
The invention provides a method for recycling ITO target waste, which is mainly used for recycling ITO waste with indium oxide content of 90-95%, screening ITO powder, and carrying out ball milling on powder with the size smaller than 1mm and indium oxide to produce an ITO target with low tin dioxide content. The method omits the process of converting waste materials into metal indium and then producing indium oxide, thereby greatly reducing the production cost. The invention produces ITO target material with low content of stannic oxide, such as 97/3ITO target material, through ball milling, the produced 97/3 target material has relative density of 99.7% and grain size of 10 μm. The technology removes a degreasing process of recovered powder, directly emulsifies and sands, shortens a recovery process of waste materials, reduces production cost and improves economic benefits.
Description
Technical Field
The invention relates to the technical field of electronic ceramic materials, in particular to a method for recycling ITO target waste.
Background
Indium tin oxide target (ITO target) is an electronic ceramic material and is mainly used for magnetron sputtering coating of ITO films. Indium tin oxide targets are mainly classified into two types of targets: planar targets and rotary targets. The targets of 90/10, 93/7 and 95/5(90/10 refers to the mass ratio of indium oxide to tin oxide) are widely used, and a large amount of residual materials are generated in the process of preparing the rotary target. Such as: after the ITO slurry is subjected to spray drying and cold isostatic pressing, the surface of the target blank is uneven, lathe machining needs to be carried out through a lathe, and a large amount of excess materials are generated during machining, wherein the amount of the excess materials is about more than 10% of the lathe excess materials.
The residual powder is usually refined into refined indium again through a recovery process, and indium oxide and ITO powder are produced, so that the production cost is greatly increased. In order to reduce the production cost of the ITO target, the generation of lathe excess materials is reduced on one hand, and the cost of excess material recycling is reduced on the other hand. 90/10, 93/7 and 95/5ITO target excess materials are recycled to produce the ITO target with the same proportion and the relative density of 95 percent, which is difficult to reach the requirement.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a method for recycling ITO target waste.
In order to achieve the purpose, the invention adopts the technical scheme that:
a recycling method of ITO target scrap comprises the following steps:
(1) screening: collecting ITO lathe waste for screening, selecting a screen with the screen aperture smaller than 1mm, collecting ITO target waste with the particle size smaller than 1mm, crushing the target waste with the particle size larger than 1mm, and then screening again;
(2) emulsifying and sanding the ITO powder collected in the step (1), wherein the rotating speed of an emulsifying machine is 5000-8000 rpm, the particle size of the ITO powder is measured by a Malvern laser particle size analyzer, and when the particle size D50 of the ITO powder is less than 0.2 mu m and the particle size D90 of the ITO powder is less than 0.5 mu m, the ITO powder is qualified, and sanding is stopped;
(3) emulsifying and sanding the indium oxide powder, determining the particle size of the indium oxide powder by using a Malvern laser particle size analyzer, and stopping sanding when the particle size D50 of the indium oxide powder is less than 0.2 mu m and the particle size D90 of the indium oxide powder is less than 0.5 mu m;
(4) mixing and sanding the ITO slurry obtained in the step (2) and the indium oxide slurry obtained in the step (3), and adding a binder to continue sanding for 30-60 min when the particle size D50 of the mixed slurry is less than 0.2 mu m and D90 of the mixed slurry is less than 0.5 mu m;
(5) drying the mixed slurry prepared in the step (4) to enable the water content of the mixed slurry to be 0.2-0.5% to obtain an ITO green compact;
(6) transferring the ITO green body into a mold, and carrying out cold isostatic pressing;
(7) heating the target blank pressed in the step (6) from 150 ℃ to 500 ℃ for degreasing sintering, and keeping the temperature of 100-150 ℃ per liter for 1-5 h in the heating process; after degreasing and sintering, carrying out first temperature rise sintering, wherein the first temperature rise sintering is to increase the temperature from 500 ℃ to 1200 ℃ for sintering, and the temperature is kept for 1-5 h when the temperature is increased to 900 ℃, 1100 ℃ and 1200 ℃ in the temperature rise process; after the first temperature rise sintering, carrying out second temperature rise sintering, wherein the second temperature rise sintering is sintering by raising the temperature from 1200 ℃ to 1600 ℃, and the temperature is kept for 1-10 h at 100-150 ℃ per liter in the temperature rise process; introducing oxygen in the sintering process, wherein the oxygen flow is 50-100L/min;
(8) and after the heat preservation is finished, cooling to 1350-1400 ℃, then heating to 1550-1600 ℃, and preserving heat for 1-5 h to obtain the ITO target.
The invention provides a method for recycling waste materials in an ITO target production process, which is mainly used for recycling ITO waste materials with indium oxide content of 90-95%, screening ITO powder, and carrying out ball milling on powder with the particle size smaller than 1mm and indium oxide to produce an ITO target with low tin dioxide content. The method omits the process of converting waste materials into metal indium and then producing indium oxide, thereby greatly reducing the production cost.
As a preferable technical scheme, in the emulsifying and sanding process in the step (2), a dispersing agent and water are added, wherein the dispersing agent accounts for 0.1-2% of the weight of the ITO powder, and the water accounts for 30-40% of the weight of the ITO powder; the dispersing agent is a mixture of an amino alcohol dispersing agent and ammonia water.
As a preferable technical scheme, in the emulsifying and sanding process in the step (3), a dispersing agent and water are added, wherein the dispersing agent accounts for 0.5-2% of the weight of the indium oxide powder, and the water accounts for 20-40% of the weight of the indium oxide powder; the dispersing agent is a mixture of an amino alcohol dispersing agent and ammonia water.
As a preferable technical scheme of the invention, the drying temperature in the step (5) is 200-250 ℃.
As a preferable technical scheme of the invention, the pressure in the step (6) is 300-400 MPa. The inventors have found through research that if the pressure is too low, the green body density is low, which in turn results in a low sintered target density.
As a preferred technical scheme of the invention, in the step (7), the heating rate of degreasing sintering is 0.2-0.5 ℃/min; the temperature rise rate of the first temperature rise sintering is 0.1-0.5 ℃/min; the temperature rise rate of the second temperature rise sintering is 0.1-0.3 ℃/min. The inventors have chosen the rate of temperature increase of this solution because if the rate of temperature increase is too fast, degreasing is incomplete and the resulting target material is prone to cracking.
As a preferred technical scheme of the invention, in the step (8), the temperature is reduced to 1350-1400 ℃ at a cooling rate of 0.5-1 ℃/min; heating to 1550-1600 ℃ at a heating rate of 0.1-0.5 ℃/min. The invention can promote the shrinkage of the aperture in the target material by adding the working procedures of one-step temperature reduction and then temperature rise sintering, thereby improving the density of the target material.
As a preferred technical scheme of the invention, the relative density of the ITO target material obtained in the step (8) is more than 99.7%, and the purity is more than 99.99%.
As a preferred technical proposal of the invention, In the ITO target material obtained In the step (8)2O3/SnO2The mass ratio was 97/3. According to the scheme, ITO target materials with low tin dioxide content, such as 97/3ITO target materials, are produced by ball milling ITO waste materials with indium oxide content of 90-95%, the relative density of the produced 97/3 target materials can reach 99.7%, and the grain size is 10 microns.
Compared with the prior art, the invention has the following beneficial effects: the technology produces ITO target material with low content of stannic oxide, such as 97/3ITO target material, by ball milling ITO waste material with indium oxide content of 90-95%, the produced 97/3 target material has relative density of 99.7% and grain size of 10 μm. The technology removes a degreasing process of recovered powder, directly emulsifies and sands, shortens a recovery process of waste materials, reduces production cost and improves economic benefits.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
Example 1
The invention relates to a recycling method of ITO target waste, which comprises the following steps:
(1) weighing 14.5kg of 90/10ITO powder with the particle size less than 1mm, emulsifying and sanding, adding 0.5 percent of dispersant (the dispersant is a mixture of amino alcohol dispersant and ammonia water) and 30 percent of pure water accounting for 90/10 percent of the weight of the ITO powder, sanding for 2 hours, detecting Malvern, and when the particle size of the powder D50 is less than 0.2 mu m and D90 is less than 0.5 mu m, determining that sanding is qualified;
(2) weighing 34kg of indium oxide, emulsifying, adding a dispersing agent (the dispersing agent is a mixture of an amino alcohol dispersing agent and ammonia water) accounting for 1.5 percent of the weight of the indium oxide powder and pure water accounting for 20 percent of the weight of the indium oxide powder, sanding for 2 hours after emulsification, detecting Malvern, and stopping sanding when the particle size D50 of the powder is less than 0.2 mu m and D90 is less than 0.5 mu m;
(3) adding the emulsified 90/10ITO slurry into the indium oxide slurry after sanding, adding a binder accounting for 3.5 percent of the weight of the mixed slurry to fully and uniformly mix the components, and detecting the content of the tin dioxide slurry to be 2.98 percent.
(4) Spray drying 97/3ITO slurry at 250 deg.C to obtain 97/3ITO powder, transferring 97/3ITO powder into a mold, and cold isostatic pressing at 400MPa to obtain ITO powder with density of 4.5g/cm3Left and right target blank bodies.
(5) Sintering the target blank, degreasing and sintering at 150-500 ℃, wherein the heating rate is 0.5 ℃/min, and the temperature is kept at 250 ℃, 400 ℃ and 500 ℃ for 1 hour. And continuously heating to 500-1200 ℃ for sintering, wherein the heating rate is 0.3 ℃/min, and the temperature is respectively kept at 900 ℃, 1100 ℃ and 1200 ℃ for 3 hours. And continuously heating to 1200-1580 ℃. The heating rate is 0.25 ℃/min, the temperature is kept for 4 hours at 1350 ℃ and 1450 ℃, and the temperature is kept for 8 hours at 1580 ℃. Introducing oxygen in the sintering process
(6) After the heat preservation is finished, the temperature is reduced to 1350 ℃ at the speed of 0.5 ℃/min, the temperature is increased to 1590 ℃ at the speed of 0.25 ℃/min, the heat preservation is carried out for 5 hours, and oxygen is introduced in the sintering process.
(7) And cooling to room temperature at the speed of 2 ℃/min after the heat preservation is finished to obtain 97/3ITO target material. The relative density was found to be 99.75%, the resistivity was found to be 110. mu. omega. cm by the four-probe method, and the purity was 4N.
Example 2
The invention relates to a recycling method of ITO target waste, which comprises the following steps:
(1) weighing 25kg of 93/7ITO powder with the particle size less than 1mm, emulsifying, grinding with a grinder, adding 1% of dispersant, grinding for 2 hours, detecting by a CPS nanometer particle size analysis system, and detecting that the CPS is qualified when the particle size of the powder D50 is less than 0.2 mu m and the particle size of D90 is less than 0.5 mu m;
(2) weighing 34kg of indium oxide, emulsifying, adding 1.5% of dispersant, sanding for 2 hours after emulsification, detecting Malvern, and determining the powder to be qualified when the particle size D50 is less than 0.2 μm and D90 is less than 0.5 μm;
(3) 93/7ITO slurry of the emulsified ITO is added into the indium oxide after sanding, 3.5 percent of binder is added, so that the indium oxide and ITO powder particles become thin, the components are fully and uniformly mixed, and the content of tin dioxide slurry is 3.05 percent.
(4) Carrying out spray drying on the ITO slurry at the spray drying temperature of 250 ℃ to obtain 97/3ITO powder; transferring the 97/3ITO powder into a mold, and carrying out cold isostatic pressing at 400MPa to obtain the ITO powder with the density of 4.5g/cm3Left and right target blank bodies.
(5) Sintering the target blank, degreasing and sintering at 150-500 ℃, wherein the heating rate is 0.5 ℃/min, and the temperature is kept at 250 ℃, 400 ℃ and 500 ℃ for 1 hour. And continuously heating to 500-1200 ℃ for sintering, wherein the heating rate is 0.3 ℃/min, and the temperature is respectively kept at 900 ℃, 1100 ℃ and 1200 ℃ for 3 hours. Continuously heating to 1200-1600 ℃, heating rate of 0.25 ℃/min, keeping the temperature at 1350 ℃ and 1450 ℃ for 4 hours, and keeping the temperature at 1560 ℃ for 8 hours. Oxygen is introduced during the sintering process.
(6) After the heat preservation is finished, the temperature is reduced to 1350 ℃ at the speed of 0.5 ℃/min, the temperature is increased to 1580 ℃ at the speed of 0.25 ℃/min, the heat preservation is carried out for 4 hours, and oxygen is introduced in the sintering process.
(7) And cooling to room temperature at the speed of 2 ℃/min after the heat preservation is finished to obtain 97/3ITO target material. The relative density was found to be 99.78%, the resistivity was found to be 113. mu. omega. cm by the four-probe method, and the purity was 4N.
Example 3
The invention relates to a recycling method of ITO target waste, which comprises the following steps:
(1) weighing 45kg of 95/5ITO powder with the particle size less than 1mm, emulsifying and sanding, adding 2% of dispersing agent, sanding for 4 hours, detecting CPS, and determining that the powder is qualified when the particle size D50 is less than 0.2 mu m and the particle size D90 is less than 0.5 mu m;
(2) weighing 30kg of indium oxide for emulsification, adding 1.5% of dispersing agent, sanding for 2 hours after emulsification, detecting Malvern, and determining the product to be qualified when the particle size D50 of the powder is less than 0.2 μm and D90 is less than 0.5 μm;
(3) 95/5ITO slurry of the emulsified ITO is added into the indium oxide powder after sanding, 4 percent of binder is added, so that the indium oxide and the ITO powder become thin, the components are fully and uniformly mixed, and the content of the tin dioxide slurry is 2.98 percent.
(4) Spray drying the ITO slurry at 250 deg.C to obtain 97/3ITO powder, transferring 97/3ITO powder into a mold, and cold isostatic pressing at 400MPa to obtain ITO powder with density of 4.5g/cm3Left and right target blank bodies.
(5) Sintering the target blank, degreasing and sintering at 150-500 ℃, wherein the heating rate is 0.5 ℃/min, and the temperature is kept at 250 ℃, 400 ℃ and 500 ℃ for 1 hour. And continuously heating to 500-1200 ℃ for sintering, wherein the heating rate is 0.3 ℃/min, and the temperature is respectively kept at 900 ℃, 1100 ℃ and 1200 ℃ for 3 hours. Continuously heating to 1200-1600 ℃, heating rate of 0.25 ℃/min, keeping the temperature at 1350 ℃ and 1450 ℃ for 4 hours, and keeping the temperature at 1550 ℃ for 10 hours. Oxygen is introduced during the sintering process.
(6) After the heat preservation is finished, the temperature is reduced to 1350 ℃ at the speed of 0.5 ℃/min, the temperature is increased to 1580 ℃ at the speed of 0.25 ℃/min, the heat preservation is carried out for 5 hours, and oxygen is introduced in the sintering process.
(7) And cooling to room temperature at the speed of 2 ℃/min after the heat preservation is finished to obtain 97/3ITO target material. The relative density was found to be 99.79%, the resistivity was found to be 115. mu. omega. cm by the four-probe method, and the purity was 4N.
Comparative example 1
The only difference between the comparative example and the example 1 is that: the ITO target scrap (90/10) and the indium oxide powder of this comparative example were spray-dried without being subjected to emulsification and sanding. The obtained 97/3ITO target material tin dioxide is not uniformly distributed, and the performance of the coating film is influenced. Because the emulsification sanding can make indium oxide and tin oxide misce bene, if do not pass emulsification sanding, can not direct spray drying, finally make the inhomogeneous of tin dioxide distribution.
Comparative example 2
The only difference between the comparative example and the example 1 is that the heating rate of all sintering processes of the comparative example is 1 ℃/min. The obtained 97/3ITO target material has low density, more cavities and cracking of the target material when the temperature rise rate is too high.
Comparative example 3
The only difference between the comparative example and the example 1 is that the comparative example does not undergo the temperature-reducing and temperature-raising sintering process (i.e., the step (6) of the example). The obtained 97/3ITO target has low density, the sintering qualification rate of the target is only 50 percent, and the production cost is high.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A method for recycling ITO target scrap is characterized by comprising the following steps:
(1) screening: collecting ITO target waste with the particle size of less than 1mm, crushing the ITO target waste with the particle size of more than 1mm, and then sieving the crushed ITO target waste again;
(2) emulsifying and sanding the ITO powder collected in the step (1), and stopping sanding when the particle size D50 of the ITO powder is less than 0.2 mu m and D90 is less than 0.5 mu m;
(3) emulsifying and sanding the indium oxide powder, and stopping sanding when the particle size D50 of the indium oxide powder is less than 0.2 mu m and D90 is less than 0.5 mu m;
(4) mixing and sanding the ITO slurry obtained in the step (2) and the indium oxide slurry obtained in the step (3), and adding a binder to continue sanding for 30-60 min when the particle size D50 of the mixed slurry is less than 0.2 mu m and D90 of the mixed slurry is less than 0.5 mu m;
(5) drying the mixed slurry prepared in the step (4) to enable the water content of the mixed slurry to be 0.2-0.5% to obtain an ITO green compact;
(6) carrying out cold isostatic pressing on the ITO green body;
(7) heating the target blank pressed in the step (6) from 150 ℃ to 500 ℃ for degreasing sintering, and keeping the temperature of 100-150 ℃ per liter for 1-5 h in the heating process; after degreasing and sintering, carrying out first temperature rise sintering, wherein the first temperature rise sintering is to increase the temperature from 500 ℃ to 1200 ℃ for sintering, and the temperature is kept for 1-5 h when the temperature is increased to 900 ℃, 1100 ℃ and 1200 ℃ in the temperature rise process; after the first temperature rise sintering, carrying out second temperature rise sintering, wherein the second temperature rise sintering is sintering by raising the temperature from 1200 ℃ to 1600 ℃, and the temperature is kept for 1-10 h at 100-150 ℃ per liter in the temperature rise process; introducing oxygen in the sintering process, wherein the oxygen flow is 50-100L/min;
(8) and after the heat preservation is finished, cooling to 1350-1400 ℃, then heating to 1550-1600 ℃, and preserving heat for 1-5 h to obtain the ITO target.
2. The method for recycling the ITO target waste material according to claim 1, wherein a dispersing agent and water are added in the emulsifying and sanding process in the step (2), wherein the dispersing agent accounts for 0.1-2% of the weight of the ITO powder, and the water accounts for 30-40% of the weight of the ITO powder; the dispersing agent is a mixture of an amino alcohol dispersing agent and ammonia water.
3. The method for recycling the ITO target waste material according to claim 1, wherein in the step (3), a dispersing agent and water are added in the process of emulsification and sanding, wherein the dispersing agent accounts for 0.5-2% of the weight of the indium oxide powder, and the water accounts for 20-40% of the weight of the indium oxide powder; the dispersing agent is a mixture of an amino alcohol dispersing agent and ammonia water.
4. The method for recycling the ITO target waste according to claim 1, wherein in the step (4), the added binder is a polyvinyl alcohol binder, and the added amount of the polyvinyl alcohol binder is 2-5% of the weight of the mixed slurry.
5. The method for recycling the ITO target scrap according to claim 1, wherein the drying temperature in the step (5) is 200 to 250 ℃.
6. The method for recycling the ITO target waste according to claim 1, wherein the pressure in the step (6) is 300 to 400 MPa.
7. The method for recycling the ITO target waste according to claim 1, wherein in the step (7), the temperature rise rate of degreasing and sintering is 0.2-0.5 ℃/min; the temperature rise rate of the first temperature rise sintering is 0.1-0.5 ℃/min; the temperature rise rate of the second temperature rise sintering is 0.1-0.3 ℃/min.
8. The method for recycling the ITO target waste according to claim 1, wherein in the step (8), the temperature is reduced to 1350-1400 ℃ at a cooling rate of 0.5-1 ℃/min; heating to 1550-1600 ℃ at a heating rate of 0.1-0.5 ℃/min.
9. The method for recycling the ITO target waste according to claim 1, wherein the ITO target obtained in step (8) has a relative density of more than 99.7% and a purity of more than 99.99%.
10. The method for recycling the ITO target waste according to claim 1, wherein In the ITO target obtained In the step (8)2O3/SnO2The mass ratio was 97/3.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115894009A (en) * | 2022-11-14 | 2023-04-04 | 先导薄膜材料（广东）有限公司 | Rapid sintering and degreasing method for ITO (indium tin oxide) planar target and supporting plate used by rapid sintering and degreasing method |
| CN116216770A (en) * | 2022-12-15 | 2023-06-06 | 先导薄膜材料（广东）有限公司 | Blue IZO powder and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101844927A (en) * | 2010-05-28 | 2010-09-29 | 电子科技大学 | High-low temperature circular sintering method for electronic ceramic materials |
| CN105481360A (en) * | 2015-11-27 | 2016-04-13 | 全椒君鸿软磁材料有限公司 | Preparation method of high saturation magnetic flux density soft magnetic ferrite magnetic core material |
| CN107129277A (en) * | 2017-04-07 | 2017-09-05 | 中国船舶重工集团公司第七二五研究所 | A kind of useless targets of ITO reclaim the method that powder prepares ITO target |
| CN108863399A (en) * | 2018-07-26 | 2018-11-23 | 深圳市东川技术研究有限公司 | Match the sintering process of grand electric heating new material |
| CN112851376A (en) * | 2020-12-31 | 2021-05-28 | 中国建筑材料科学研究总院有限公司 | High-density fine-grain ceramic and preparation method and application thereof |
| CN113149611A (en) * | 2021-05-17 | 2021-07-23 | 先导薄膜材料（广东）有限公司 | ITO powder prepared by recycling ITO waste target blank, target material and preparation method thereof |
| CN113233871A (en) * | 2021-04-25 | 2021-08-10 | 先导薄膜材料（广东）有限公司 | Method for preparing ITO evaporation material from ITO residual target reclaimed material |
-
2022
- 2022-01-11 CN CN202210029115.8A patent/CN114409380A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101844927A (en) * | 2010-05-28 | 2010-09-29 | 电子科技大学 | High-low temperature circular sintering method for electronic ceramic materials |
| CN105481360A (en) * | 2015-11-27 | 2016-04-13 | 全椒君鸿软磁材料有限公司 | Preparation method of high saturation magnetic flux density soft magnetic ferrite magnetic core material |
| CN107129277A (en) * | 2017-04-07 | 2017-09-05 | 中国船舶重工集团公司第七二五研究所 | A kind of useless targets of ITO reclaim the method that powder prepares ITO target |
| CN108863399A (en) * | 2018-07-26 | 2018-11-23 | 深圳市东川技术研究有限公司 | Match the sintering process of grand electric heating new material |
| CN112851376A (en) * | 2020-12-31 | 2021-05-28 | 中国建筑材料科学研究总院有限公司 | High-density fine-grain ceramic and preparation method and application thereof |
| CN113233871A (en) * | 2021-04-25 | 2021-08-10 | 先导薄膜材料（广东）有限公司 | Method for preparing ITO evaporation material from ITO residual target reclaimed material |
| CN113149611A (en) * | 2021-05-17 | 2021-07-23 | 先导薄膜材料（广东）有限公司 | ITO powder prepared by recycling ITO waste target blank, target material and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115894009A (en) * | 2022-11-14 | 2023-04-04 | 先导薄膜材料（广东）有限公司 | Rapid sintering and degreasing method for ITO (indium tin oxide) planar target and supporting plate used by rapid sintering and degreasing method |
| CN116216770A (en) * | 2022-12-15 | 2023-06-06 | 先导薄膜材料（广东）有限公司 | Blue IZO powder and preparation method thereof |
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